CA1128961A - Process for preparing 3-(3,5-di-tert alkyl-4- hydroxyphenyl)-2,2-di-substituted propionaldehydes - Google Patents
Process for preparing 3-(3,5-di-tert alkyl-4- hydroxyphenyl)-2,2-di-substituted propionaldehydesInfo
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- CA1128961A CA1128961A CA357,170A CA357170A CA1128961A CA 1128961 A CA1128961 A CA 1128961A CA 357170 A CA357170 A CA 357170A CA 1128961 A CA1128961 A CA 1128961A
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- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
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- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
- C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
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Abstract
Abstract A PROCESS FOR PREPARING 3-(3,5-DI-TERT.ALKYL-4-HYDROXY-PHENYL)-2,2-DI-SUBSTITUTED PROPIONALDEHYDES
There is disclosed a process comprising reacting a compound having the general structural Formula II:
II
with a compound having the general Formula III:
III
in the presence of a basic catalyst while dissolved in an organic solvent to yield an aldehyde having the structural Formula I:
I
wherein R1 and R2 are the same or different radicals selected from the group consisting of tertiary alkyl radicals having from 4 to 12 carbon atoms, R3 and R4 are the same or different radicals selected from the group consisting of alkyl radicals containing from 1 to 12 carbon atoms, cycloalkyl radicals containing from 5 to 12 carbon atoms,phenyl and substituted phenyl radicals or R3 and R4 with the carbon atom to which they are joined may form a cycloalkyl ring of from 5 to 12 carbon atoms, R5 is selected from the group consisting of hydrogen, alkyl radicals containing from 1 to 12 carbon atoms, or a cycloalkyl radical containing 5 or 6 carbon atoms.
There is disclosed a process comprising reacting a compound having the general structural Formula II:
II
with a compound having the general Formula III:
III
in the presence of a basic catalyst while dissolved in an organic solvent to yield an aldehyde having the structural Formula I:
I
wherein R1 and R2 are the same or different radicals selected from the group consisting of tertiary alkyl radicals having from 4 to 12 carbon atoms, R3 and R4 are the same or different radicals selected from the group consisting of alkyl radicals containing from 1 to 12 carbon atoms, cycloalkyl radicals containing from 5 to 12 carbon atoms,phenyl and substituted phenyl radicals or R3 and R4 with the carbon atom to which they are joined may form a cycloalkyl ring of from 5 to 12 carbon atoms, R5 is selected from the group consisting of hydrogen, alkyl radicals containing from 1 to 12 carbon atoms, or a cycloalkyl radical containing 5 or 6 carbon atoms.
Description
28g6.~
A PROCESS FOR PREPARING 3-(3,5-DI-TERT.ALKYL-4-HYDROXYPHENYL)-2,2-DI-SUBSTITUTED PROPIONALDEHYDES
Technical Field -This invention relates to a novel and useful process for the preparation of certain 3-(3,5-di-tert.alkyl-4-hydroxyphenyl)-2,2-di-substituted propionaldehydes, hereinafter known as 3HP compounds. In particular, the invention concerns the preparation o~ the compounds of Formula I:
~ _~ R3 ~ H
R2 2 R ~ O
wherein Rl and R2 are the same or different radicals selected from the group consisting of tertiary alkyl 15radicals having from 4 to 12 carbon atoms, R3 and R4 are the same or different radicals selected from the group consisting of alkyl radicals containing from 1 to 12 carbon atoms, cycloalkyl radicals containing from 5 to 12 carbon atoms, phenyl and phenyl radicals substituted by 1 to 3 alkyl radicals each of which contains 1 to 4 carbon atoms or R3 and R4 with the carbon atom to which they are joined may form a cyclo-alkyl ring of from 5 to 12 carbon atoms.
Back~round Art The 3 HP compounds of Formula I are useful as stabilizers in organic material normally subject to deterioration caused by heat, light and oxygen. In addition to being antioxidants they are e~en more useful as intermediates for the preparation of high molecular weight antioxidants for polypropylene and other sub-strates.
a .
A PROCESS FOR PREPARING 3-(3,5-DI-TERT.ALKYL-4-HYDROXYPHENYL)-2,2-DI-SUBSTITUTED PROPIONALDEHYDES
Technical Field -This invention relates to a novel and useful process for the preparation of certain 3-(3,5-di-tert.alkyl-4-hydroxyphenyl)-2,2-di-substituted propionaldehydes, hereinafter known as 3HP compounds. In particular, the invention concerns the preparation o~ the compounds of Formula I:
~ _~ R3 ~ H
R2 2 R ~ O
wherein Rl and R2 are the same or different radicals selected from the group consisting of tertiary alkyl 15radicals having from 4 to 12 carbon atoms, R3 and R4 are the same or different radicals selected from the group consisting of alkyl radicals containing from 1 to 12 carbon atoms, cycloalkyl radicals containing from 5 to 12 carbon atoms, phenyl and phenyl radicals substituted by 1 to 3 alkyl radicals each of which contains 1 to 4 carbon atoms or R3 and R4 with the carbon atom to which they are joined may form a cyclo-alkyl ring of from 5 to 12 carbon atoms.
Back~round Art The 3 HP compounds of Formula I are useful as stabilizers in organic material normally subject to deterioration caused by heat, light and oxygen. In addition to being antioxidants they are e~en more useful as intermediates for the preparation of high molecular weight antioxidants for polypropylene and other sub-strates.
a .
2,&~
la Other methods for the preparation of the aldehydes obtained from -the process of this invention are described in British Paten-t 1,455,766 and in U.S. 4,091,225. Both the British and the U.S. Patents claim a process in which 3,5-di-tert.butyl-4-hydroxybenzyl chloride is reacted with isobutyraldehyde under phase transfer con-ditions. The British Patent describes the product as a red-brown oil, however, the process disclosed in the U.S. Patent j~,~
. ., 1~L;?J8~
avoids discoloration of the product by carrying out the process under an atmosphere of nitrogen.
A difficulty with use of benzyl chloride as taught in the prior art is that a possible coproduct in the prepar-5 ation of the benzyl chloride is bis(chloromethyl) ether,which is known to be carcinogenic. Thus, it is highly desirable to find other compounds and processes which are capable of forming the desired aldehyde without the use of the benzyl chloride.
me process of the present invention is superior to these in that it produces a light yellow solid product even when carried out in an atmosphere of air. In addition, the art described in the references requires that a mixture of the reactants be added slowly (greater than 2 hours) to the reaction medium. In the process of the present invention it is preferred that the aldehyde not be added until the reaction mixture has been heated to the desired temperature;
then the aldehyde may be added in a rapid manner, (10 to 15 minutes), not as taught and disclosed in the prior art references. It has been determined that the aldehyde may in fact be added all at once without having any appreciable effect on either the yield or purity of the desired product.
British Patent 1,455,766 also claims a process in which a 3,5-di-tert.butyl-4-hydroxybenzyl-N,N-dialkyldithiocarbam-ate is reacted with isobutyraldehyde. The British process gives a higher yield and a purer product than the other processes described. However, the yield is still not as high as that obtained from the process of the present invention.
Another advantage of the process of the present inven-tion over the prior art is that it does not require the use of highly flammable carbon disulfide, one of the reactants needed to form the dithiocarbamate in the above-referenced patent.
The only known reference to 2,6-di-tert.butyl-4-alkoxy-methylphenyl in the alkylation of an active hydrogen compound is U.S. Patent 4,014,943. In this patent the compound alkylated is nitromethane and the yield of the product after removing insoluble material is only 65~. U.S. Patent 4,014,943 also teaches the use of equimolar amounts o~
base and nitro compounds while the process of the present invention can be carried out using as little as 3 mole percent of base.
It is the novel and use~ul process for the prepara-tion of 3HP compounds using 2,6-di-tert.butyl-4-methoxy-methylphenol as a highly effective alkylating agent for aldehydes which have only one hydrogen on the carbon adjacent to the carbonyl group that forms the basis of this învention. The product yields using the processes of this invention are greater than 95% in all cases and the purity of the desired product is high.
Disclosure of the Invention A process comprising reacting a compound having the general structural Formula II:
1 ~ .
OH ~ O ~ H20-R5 (II) 20R "-~~~~
with a compound having the general structural Formula III:
~ O
25 ~ CH-CH (III) in the presence of a basic catalyst while dissolved in an organic solvent to yield an aldehyde having the general structural Formula I
OH- ~ R3 / (Il wherein Rl and R2 are the same or different radicals selected from the group consisting of tertiary alkyl -radicals having from 4 to 12 carbon atoms, R3 and R4 are the same or different radicals selected from the ~ group consisting of alkyl radicals containing from 1 .. ~,.~ .
3a to 12 carbon atoms, cycloalkyl radicals containing from 5 to 12 carbon a-toms, phenyl and phenyl radicals substi.-tuted by 1 to 3 alkyl radicals each of which contains 1 to 4 carbon atoms or R3 and R4 with the carbon a-tom to which they are joined may form a cycloalkyl ring of from 5 to 12 carbon atoms, R5 is selected from the group consisting of hydrogen, alkyl radicals containing from 1 to 12 carbon atoms, or a cycloalkyl radical containing 5 or 6 carbon atoms.
1~&~
Detailed Description The reaction is carried out in solvents such as aliphatic alcohols which are water soluble, such as methanol, ethanol and 2-propanol, and aliphatic ethers such as tetrahydrofuran and aliphatic nitriles such as acetonitrile.
The reaction is carried out at a temperature from 20C. to the boiling point of the solvent. Preferably the reaction is conducted at solvent reflux temperature.
Suitable catalysts for the reaction are the alkali hydroxides and alkoxides such as sodium hydroxide, sodium methoxide, potassium hydroxide and potassium tert.butox-ide. The amount of base catalyst used in the reactions of this invention may range from 2.5 to 100 mole percent relative to the phenol, although from 5 to 15 mole percent is the preferred range.
The highest yield of product is obtained using from 5 to 25 percent excess of the aldehyde to the alkoxymethyl-phenol.
Representative examples of the compounds of Formula II which are useful in the present invention are -the following: 3,5-di-tert.butyl-4-hydroxybenzyl alcohol~
2,6-di-tert.butyl-4-methoxymethylphenol, 2,6-di-tert.
butyl-4-isopropoxymethylphenol, 2,6-di-tert.butyl-4-ethoxy-methylphenol, 2,6-di-tert.hexyl-4-methoxymethylphenol, 2,6-di-tert.pentyl-4-hydroxymethylphenol, 2,6-di-tert.butyl-4-butoxymethylphenol, 2,6-di-tert.butyl-4-hexyloxymethyl-phenol and 2,6-di-tert.butyl-4-octyloxymethylphenol.
Compounds of Formula III are prepared by well-known reactions and they are also available commercially. Repre-sentative of compounds of Formula III which are useful in the the present invention are the following: isobutyraldehyde, 2-ethylbutyraldehyde, 2-ethylhexanal and cyclohexane-carboxaldehyde.
The process of this invention can be generally des-cribed as heating a solution of a compound of Formula II, and a compound of Formula III and a base under reflux for from 2 to 6 hours. The base is then neutralized and the reaction mixture is poured into water. Solid products are isolated , ,~ ;, .
8~
by filtration and liquid products by extraction followed by evaporation. The invention is further illustrated by reference to the following examples, which are intended to be representative rather than restrictive of the 5 scope of this invention.
Best Mode For Carryin~ Out me Invention Example 1 A solution of 25 grams (0.1 mole) of 2,6-di-tert.butyl-4-methoxymethylphenol and one gram (0.015 mole) of KOH in 100 milliliters of methanol was heated to 60C. 9 grams (0.125 moles) of isobutyraldehyde was added to the solution during a period of 10 minutes and the reaction mixture 15 was heated under reflux for 3 hours. After the mixture had cooled to room temperature it was poured into 125 milliliters of 1% acetic acid. me solid that precipitated was filtered off and allowed to dry. mere was obtained 28.5 grams (98.2% of theory) of 2,2-dimethyl-3-(3,5-di-tert.butyl-20 4-hydroxyphenyl) propionaldehyde with a melting point of 72 to 74C.
Effect of the solvent and base used in Example 1, ( me reaction of 2,6-di-tert.butyl-4-methoxymethyl phenol with isobutyraldehyde) was examined with the results shown in 25 Table 1:
Table I
Effect of Solvent and Base in Example 1 ExamPle Solvent Base (1 ~ram) %Yield M.P.(C.) 30 1 Methanol KOH 98.2 72-74 2 Methanol KOH(0.2 gm.) 98.8 68-71
la Other methods for the preparation of the aldehydes obtained from -the process of this invention are described in British Paten-t 1,455,766 and in U.S. 4,091,225. Both the British and the U.S. Patents claim a process in which 3,5-di-tert.butyl-4-hydroxybenzyl chloride is reacted with isobutyraldehyde under phase transfer con-ditions. The British Patent describes the product as a red-brown oil, however, the process disclosed in the U.S. Patent j~,~
. ., 1~L;?J8~
avoids discoloration of the product by carrying out the process under an atmosphere of nitrogen.
A difficulty with use of benzyl chloride as taught in the prior art is that a possible coproduct in the prepar-5 ation of the benzyl chloride is bis(chloromethyl) ether,which is known to be carcinogenic. Thus, it is highly desirable to find other compounds and processes which are capable of forming the desired aldehyde without the use of the benzyl chloride.
me process of the present invention is superior to these in that it produces a light yellow solid product even when carried out in an atmosphere of air. In addition, the art described in the references requires that a mixture of the reactants be added slowly (greater than 2 hours) to the reaction medium. In the process of the present invention it is preferred that the aldehyde not be added until the reaction mixture has been heated to the desired temperature;
then the aldehyde may be added in a rapid manner, (10 to 15 minutes), not as taught and disclosed in the prior art references. It has been determined that the aldehyde may in fact be added all at once without having any appreciable effect on either the yield or purity of the desired product.
British Patent 1,455,766 also claims a process in which a 3,5-di-tert.butyl-4-hydroxybenzyl-N,N-dialkyldithiocarbam-ate is reacted with isobutyraldehyde. The British process gives a higher yield and a purer product than the other processes described. However, the yield is still not as high as that obtained from the process of the present invention.
Another advantage of the process of the present inven-tion over the prior art is that it does not require the use of highly flammable carbon disulfide, one of the reactants needed to form the dithiocarbamate in the above-referenced patent.
The only known reference to 2,6-di-tert.butyl-4-alkoxy-methylphenyl in the alkylation of an active hydrogen compound is U.S. Patent 4,014,943. In this patent the compound alkylated is nitromethane and the yield of the product after removing insoluble material is only 65~. U.S. Patent 4,014,943 also teaches the use of equimolar amounts o~
base and nitro compounds while the process of the present invention can be carried out using as little as 3 mole percent of base.
It is the novel and use~ul process for the prepara-tion of 3HP compounds using 2,6-di-tert.butyl-4-methoxy-methylphenol as a highly effective alkylating agent for aldehydes which have only one hydrogen on the carbon adjacent to the carbonyl group that forms the basis of this învention. The product yields using the processes of this invention are greater than 95% in all cases and the purity of the desired product is high.
Disclosure of the Invention A process comprising reacting a compound having the general structural Formula II:
1 ~ .
OH ~ O ~ H20-R5 (II) 20R "-~~~~
with a compound having the general structural Formula III:
~ O
25 ~ CH-CH (III) in the presence of a basic catalyst while dissolved in an organic solvent to yield an aldehyde having the general structural Formula I
OH- ~ R3 / (Il wherein Rl and R2 are the same or different radicals selected from the group consisting of tertiary alkyl -radicals having from 4 to 12 carbon atoms, R3 and R4 are the same or different radicals selected from the ~ group consisting of alkyl radicals containing from 1 .. ~,.~ .
3a to 12 carbon atoms, cycloalkyl radicals containing from 5 to 12 carbon a-toms, phenyl and phenyl radicals substi.-tuted by 1 to 3 alkyl radicals each of which contains 1 to 4 carbon atoms or R3 and R4 with the carbon a-tom to which they are joined may form a cycloalkyl ring of from 5 to 12 carbon atoms, R5 is selected from the group consisting of hydrogen, alkyl radicals containing from 1 to 12 carbon atoms, or a cycloalkyl radical containing 5 or 6 carbon atoms.
1~&~
Detailed Description The reaction is carried out in solvents such as aliphatic alcohols which are water soluble, such as methanol, ethanol and 2-propanol, and aliphatic ethers such as tetrahydrofuran and aliphatic nitriles such as acetonitrile.
The reaction is carried out at a temperature from 20C. to the boiling point of the solvent. Preferably the reaction is conducted at solvent reflux temperature.
Suitable catalysts for the reaction are the alkali hydroxides and alkoxides such as sodium hydroxide, sodium methoxide, potassium hydroxide and potassium tert.butox-ide. The amount of base catalyst used in the reactions of this invention may range from 2.5 to 100 mole percent relative to the phenol, although from 5 to 15 mole percent is the preferred range.
The highest yield of product is obtained using from 5 to 25 percent excess of the aldehyde to the alkoxymethyl-phenol.
Representative examples of the compounds of Formula II which are useful in the present invention are -the following: 3,5-di-tert.butyl-4-hydroxybenzyl alcohol~
2,6-di-tert.butyl-4-methoxymethylphenol, 2,6-di-tert.
butyl-4-isopropoxymethylphenol, 2,6-di-tert.butyl-4-ethoxy-methylphenol, 2,6-di-tert.hexyl-4-methoxymethylphenol, 2,6-di-tert.pentyl-4-hydroxymethylphenol, 2,6-di-tert.butyl-4-butoxymethylphenol, 2,6-di-tert.butyl-4-hexyloxymethyl-phenol and 2,6-di-tert.butyl-4-octyloxymethylphenol.
Compounds of Formula III are prepared by well-known reactions and they are also available commercially. Repre-sentative of compounds of Formula III which are useful in the the present invention are the following: isobutyraldehyde, 2-ethylbutyraldehyde, 2-ethylhexanal and cyclohexane-carboxaldehyde.
The process of this invention can be generally des-cribed as heating a solution of a compound of Formula II, and a compound of Formula III and a base under reflux for from 2 to 6 hours. The base is then neutralized and the reaction mixture is poured into water. Solid products are isolated , ,~ ;, .
8~
by filtration and liquid products by extraction followed by evaporation. The invention is further illustrated by reference to the following examples, which are intended to be representative rather than restrictive of the 5 scope of this invention.
Best Mode For Carryin~ Out me Invention Example 1 A solution of 25 grams (0.1 mole) of 2,6-di-tert.butyl-4-methoxymethylphenol and one gram (0.015 mole) of KOH in 100 milliliters of methanol was heated to 60C. 9 grams (0.125 moles) of isobutyraldehyde was added to the solution during a period of 10 minutes and the reaction mixture 15 was heated under reflux for 3 hours. After the mixture had cooled to room temperature it was poured into 125 milliliters of 1% acetic acid. me solid that precipitated was filtered off and allowed to dry. mere was obtained 28.5 grams (98.2% of theory) of 2,2-dimethyl-3-(3,5-di-tert.butyl-20 4-hydroxyphenyl) propionaldehyde with a melting point of 72 to 74C.
Effect of the solvent and base used in Example 1, ( me reaction of 2,6-di-tert.butyl-4-methoxymethyl phenol with isobutyraldehyde) was examined with the results shown in 25 Table 1:
Table I
Effect of Solvent and Base in Example 1 ExamPle Solvent Base (1 ~ram) %Yield M.P.(C.) 30 1 Methanol KOH 98.2 72-74 2 Methanol KOH(0.2 gm.) 98.8 68-71
3 Methanol NaOH 99.0 63-67 Methanol NaOCH3 99.6 66-69 Tetrahydrofuran KOC(CH3)3 100 61-67 35 6 Acetonitrile K C(CH3)3 97.0 68-70 me results, as shown in Table I, indicate that only a small amount of potassium hydroxide is required for this reaction to take place. me table also shows that the 8~
reaction can be run in ethers and nitriles, at least when potassium tert. butoxide is used as the base, with only a slight decrease in product purity. In addition, thè eXamples 3 and 4 indicate that sodium hydroxide and methoxide catalyze 5 the reaction as well as the potassium bases do.
Other aldehydes have been substituted in the process described in Example 1 for isobutyraldehyde. The results are shown in Table II below wherein ~ will hereinafter denote a tert.butyl radical.
Table II
O ~ CH20CH3 + ~ CHCHO~ O ~ R3 R3 R4 Yield(% of theory) M.P.
Example 7 C2H5 2H5 99.4 58.5-61C.
Example 8 C3H7 CH3 97 5 liquid Example 9 cyclohexyl* cyclohexyl* 97.2 71-75C.
*R3 and R4 together with the carbon atom to which they are joined form a cyclohexyl ring.
me following Table involves the use of 2,6-di-tert.butyl-
reaction can be run in ethers and nitriles, at least when potassium tert. butoxide is used as the base, with only a slight decrease in product purity. In addition, thè eXamples 3 and 4 indicate that sodium hydroxide and methoxide catalyze 5 the reaction as well as the potassium bases do.
Other aldehydes have been substituted in the process described in Example 1 for isobutyraldehyde. The results are shown in Table II below wherein ~ will hereinafter denote a tert.butyl radical.
Table II
O ~ CH20CH3 + ~ CHCHO~ O ~ R3 R3 R4 Yield(% of theory) M.P.
Example 7 C2H5 2H5 99.4 58.5-61C.
Example 8 C3H7 CH3 97 5 liquid Example 9 cyclohexyl* cyclohexyl* 97.2 71-75C.
*R3 and R4 together with the carbon atom to which they are joined form a cyclohexyl ring.
me following Table involves the use of 2,6-di-tert.butyl-
4-alkoxymethylphenols other than 2,6-di-tert.butyl-4-methoxy-methylphenol as the alkylating agent. The results of this 25 set of examples are shown in Table III.All runs were made in methanol using 1 gram of potassium hydroxide as the base and otherwise following Example 1.
Table III
O ~ H20-R5 ~ CHCHO----~OH ~ H2-C-CHO ~ R50H
Exam~le ~ % Yield M.P.(C.) (1) CH3 98.2 72-74 11 CH3CH2 99 0 71.5-73 12 (CH3)2CH 87.6 72-74 13 C8H17 76.8 63.5-71 As shown, high purity products were obtained from all but one of the alkylating agents. The yield and purity of the product ob~ained from the octyloxymethylphenol (Example 13) could be improved by distilling off the water insolùble
Table III
O ~ H20-R5 ~ CHCHO----~OH ~ H2-C-CHO ~ R50H
Exam~le ~ % Yield M.P.(C.) (1) CH3 98.2 72-74 11 CH3CH2 99 0 71.5-73 12 (CH3)2CH 87.6 72-74 13 C8H17 76.8 63.5-71 As shown, high purity products were obtained from all but one of the alkylating agents. The yield and purity of the product ob~ained from the octyloxymethylphenol (Example 13) could be improved by distilling off the water insolùble
5 co-product, l-octanol.
In order to illustrate the selective nature of the alkoxymethylphenols to aldehyde activated hydrogen compounds the following experiments set out in Tables IV and V were performed.
The reaction of 2,6-di-tert.butyl-4-methoxymethylphenol with active hydrogen compounds in which the activation is provided by groups other than the aldehyde group was investigated. The active hydrogen compounds used and the results of the alkylations are listed in Tables IV and V
15 below. The methanol/potassium hydroxide system was used in all runs except those in which the active hydrogen compound contained an ester group, in which case, an ethanol/
sodium ethoxide system was used to avoid transesterification of the esters. Otherwise, the procedure is as outlined in 20 Example 1.
Table IV
OH- ~ -CH20CH3 + ~ CH-X-~ O ~ CH3 Crude Product Recrystallized Product Example X % Yield M.P.(C. ~ % Yield M.P.(C.) 30 14 No2 96.7 90-97 75.6100-102.5 3 99 50-64 69.769-74 16 CN No Reaction 17 COOEt No Reaction TableI~ shows that 2,6-di-tert.butyl-4-methoxymethylphenol is a more effective alkylating agent for the aldehydes in TableII than for any other type of active hydrogen compound.
Substitution of the doubly activated compounds of Table V
for the isobutyraldehyde of Example 1 gave the following results:
Table V
OH-- ~ H2-0CH3 + CH2~ ~ OH ~ /
Example X Y Product 18 COCH3 COCH3 OH~ ~ CH CH''' 3 + COCH3 OH~ }CH2CH2C OCH3 20 19 COOEt COOEt No Reaction COOEt CN No Reaction 21 COOEt COCH3 No Reaction 22 CN CN No Reaction m e lack of reactivity of 2,6-di-tert.butyl-4-methoxy-methylphenol with the doubly activated compounds of Table 5 is rather surprising since these compounds are readily alkylated by a wide variety of alkylating agents.
30 Industrial APplicability From the results obtained in the examples, it is evident that the process of this invention will alleviate the problems of preparing compounds such as 3(3,5-di-tert.alkyl-4-hydroxyphenyl)2,2-disubstituted propionaldehydes in that 35 it avoids the necessity of reacting 3,5-di-tert.alkyl-4-hydroxybenzyl chloride in a phase transfer reaction. Also, the use of an inert atmosphere as disclosed in the prior art is obviated. In addition, a ver~y beneficial aspect of this A
8~
invention is the unusually high yield and high purity of the desired product. The process of the present invention is superior to those of the past in that the process of this invention produces a light yellow solid product wherein 5 the processes described in the references provide products of inferior purity and yield. In addition, the process of this invention has greatly lessened the preparation time of the desired product. Another advantage of the process of the present invention is that it does not require the use 10 of highly flammable carbon disulfide as taught in the prior art. The products of this process invention are useful as antioxidants for organic materials, but more importantly as intermediates for the preparation of high molecular weight polypropylene antioxidants.
While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in this art that various changes and modifications may be made therein without departing from the spirit or scope of the invention.
In order to illustrate the selective nature of the alkoxymethylphenols to aldehyde activated hydrogen compounds the following experiments set out in Tables IV and V were performed.
The reaction of 2,6-di-tert.butyl-4-methoxymethylphenol with active hydrogen compounds in which the activation is provided by groups other than the aldehyde group was investigated. The active hydrogen compounds used and the results of the alkylations are listed in Tables IV and V
15 below. The methanol/potassium hydroxide system was used in all runs except those in which the active hydrogen compound contained an ester group, in which case, an ethanol/
sodium ethoxide system was used to avoid transesterification of the esters. Otherwise, the procedure is as outlined in 20 Example 1.
Table IV
OH- ~ -CH20CH3 + ~ CH-X-~ O ~ CH3 Crude Product Recrystallized Product Example X % Yield M.P.(C. ~ % Yield M.P.(C.) 30 14 No2 96.7 90-97 75.6100-102.5 3 99 50-64 69.769-74 16 CN No Reaction 17 COOEt No Reaction TableI~ shows that 2,6-di-tert.butyl-4-methoxymethylphenol is a more effective alkylating agent for the aldehydes in TableII than for any other type of active hydrogen compound.
Substitution of the doubly activated compounds of Table V
for the isobutyraldehyde of Example 1 gave the following results:
Table V
OH-- ~ H2-0CH3 + CH2~ ~ OH ~ /
Example X Y Product 18 COCH3 COCH3 OH~ ~ CH CH''' 3 + COCH3 OH~ }CH2CH2C OCH3 20 19 COOEt COOEt No Reaction COOEt CN No Reaction 21 COOEt COCH3 No Reaction 22 CN CN No Reaction m e lack of reactivity of 2,6-di-tert.butyl-4-methoxy-methylphenol with the doubly activated compounds of Table 5 is rather surprising since these compounds are readily alkylated by a wide variety of alkylating agents.
30 Industrial APplicability From the results obtained in the examples, it is evident that the process of this invention will alleviate the problems of preparing compounds such as 3(3,5-di-tert.alkyl-4-hydroxyphenyl)2,2-disubstituted propionaldehydes in that 35 it avoids the necessity of reacting 3,5-di-tert.alkyl-4-hydroxybenzyl chloride in a phase transfer reaction. Also, the use of an inert atmosphere as disclosed in the prior art is obviated. In addition, a ver~y beneficial aspect of this A
8~
invention is the unusually high yield and high purity of the desired product. The process of the present invention is superior to those of the past in that the process of this invention produces a light yellow solid product wherein 5 the processes described in the references provide products of inferior purity and yield. In addition, the process of this invention has greatly lessened the preparation time of the desired product. Another advantage of the process of the present invention is that it does not require the use 10 of highly flammable carbon disulfide as taught in the prior art. The products of this process invention are useful as antioxidants for organic materials, but more importantly as intermediates for the preparation of high molecular weight polypropylene antioxidants.
While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in this art that various changes and modifications may be made therein without departing from the spirit or scope of the invention.
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
Claims
1. A process comprising reacting a compound having the general structural Formula II:
II
with a compound having the general Formula III:
III
in the presence of a basic catalyst while dissolved in an organic solvent to yield an aldehyde having the structural Formula I:
wherein R1 and R2 are the same or different radicals selected from the group consisting of tertiary alkyl radicals having from 4 to 12 carbon atoms, R3 and R4 are the same or different radicals selected from the group consisting of alkyl radicals containing from 1 to 12 carbon atoms, cycloalkyl radicals containing from 5 to 12 carbon atoms, phenyl and phenyl radicals substi-tuted by 1 to 3 alkyl radicals each of which contains 1 to 4 carbon atoms or R3 and R4 with the carbon atom to which they are joined may form a cycloalkyl ring of from 5 to 12 carbon atoms, R5 is selected from the group consisting of hydrogen, alkyl radicals containing from 1 to 12 carbon atoms, or a cycloalkyl radical containing 5 or 6 carbon atoms.
II
with a compound having the general Formula III:
III
in the presence of a basic catalyst while dissolved in an organic solvent to yield an aldehyde having the structural Formula I:
wherein R1 and R2 are the same or different radicals selected from the group consisting of tertiary alkyl radicals having from 4 to 12 carbon atoms, R3 and R4 are the same or different radicals selected from the group consisting of alkyl radicals containing from 1 to 12 carbon atoms, cycloalkyl radicals containing from 5 to 12 carbon atoms, phenyl and phenyl radicals substi-tuted by 1 to 3 alkyl radicals each of which contains 1 to 4 carbon atoms or R3 and R4 with the carbon atom to which they are joined may form a cycloalkyl ring of from 5 to 12 carbon atoms, R5 is selected from the group consisting of hydrogen, alkyl radicals containing from 1 to 12 carbon atoms, or a cycloalkyl radical containing 5 or 6 carbon atoms.
2. A process as described in claim 1 above wherein compounds having the general structural formula II are selected from the group consisting of 2,6-di-tert.butyl-4-methoxy-methylphenol, 2,6-di-tert.butyl-4-ethoxymethylphenol and 2,6-di-tert.butyl-4-hydroxymethylphenol.
3. A process as described in claim 1 above wherein compounds having the general formula III are slected from the group consisting of isobutyraldehyde, 2-ethylbutyralde-hyde, 2-ethylhexanal and cyclohexanecarboxaldehyde.
4. A process as described in claim 1 wherein the catalyst is selected from the group consisting of sodium hydroxide, sodium ethoxide, sodium methoxide, potassium tert.
butoxide, and potassium hydroxide.
butoxide, and potassium hydroxide.
5. A process as described in claim 1 wherein the solvent is selected from the group consisting of methanol, ethanol and 2-propanol.
6. A process comprising reacting 2,6-di-tert.butyl-4-methoxymethylphenol or 2,6-di-tert.butyl-4-hydroxymethyl-phenol with isobutyraldehyde in the presence of a basic catalyst while dissolved in an organic solvent to yield 3-(3,5-di-tert.butyl-4-hydroxyphenyl)-2,2-dimethyl-propionaldehyde.
7. A process according to claim 6 wherein the reaction is carried out at a temperature from 20°C. to the reflux mperature of the reaction mixture.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US84,490 | 1979-10-15 | ||
| US06/084,490 US4284823A (en) | 1979-10-15 | 1979-10-15 | Process for preparing 3-(3,5-di-tert.alkyl-4-hydroxy-phenyl)-2,2-di-substituted propionaldehydes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1128961A true CA1128961A (en) | 1982-08-03 |
Family
ID=22185289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA357,170A Expired CA1128961A (en) | 1979-10-15 | 1980-07-28 | Process for preparing 3-(3,5-di-tert alkyl-4- hydroxyphenyl)-2,2-di-substituted propionaldehydes |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4284823A (en) |
| EP (1) | EP0027426B1 (en) |
| JP (1) | JPS5663937A (en) |
| CA (1) | CA1128961A (en) |
| DE (1) | DE3062635D1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0433614U (en) * | 1990-07-16 | 1992-03-19 | ||
| DE4213750A1 (en) * | 1992-04-25 | 1993-10-28 | Basf Ag | Process for the preparation of 3- (hydroxyphenyl) propionaldehydes and optionally the production of 3- (hydroxyphenyl) propanols |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2947786A (en) * | 1958-04-14 | 1960-08-02 | Eastman Kodak Co | Substituted unsaturated aldehydes |
| SE7407449L (en) * | 1973-07-20 | 1975-01-21 | Ciba Geigy Ag | |
| US4091225A (en) * | 1974-01-22 | 1978-05-23 | The Goodyear Tire & Rubber Company | Antioxidant ester substituted phenols and process for their preparation |
-
1979
- 1979-10-15 US US06/084,490 patent/US4284823A/en not_active Expired - Lifetime
-
1980
- 1980-07-28 CA CA357,170A patent/CA1128961A/en not_active Expired
- 1980-09-26 EP EP80630044A patent/EP0027426B1/en not_active Expired
- 1980-09-26 DE DE8080630044T patent/DE3062635D1/en not_active Expired
- 1980-10-07 JP JP14035780A patent/JPS5663937A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| US4284823A (en) | 1981-08-18 |
| EP0027426B1 (en) | 1983-04-06 |
| JPS624375B2 (en) | 1987-01-30 |
| JPS5663937A (en) | 1981-05-30 |
| EP0027426A1 (en) | 1981-04-22 |
| DE3062635D1 (en) | 1983-05-11 |
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